TWI719153B - Dialkyl(ene) polyalkylamine compositions, derivatives thereof, a process to make them, and their use - Google Patents

Abstract

The invention relates to compositions comprising di-fatty-alkyl(ene) polyalkylamines, a process to make them, and the use thereof. The product show good performance combined with a favourable viscosity profile.

Description

Dialkyl (alkenyl) polyalkylamine composition, its derivative, its production method and its use

The present invention relates to a composition of a disaliphatic alk(en)-based polyalkylamine in which the polyalkylamine part shows a specific degree of branching, a method for manufacturing such a composition, and its use in various applications.

Alk(en)-based polyalkylamines are well known and are especially used in asphalt applications.

WO 2006/076929 discloses a completely linear product with a fatty alkyl moiety, which serves as an intermediate in the synthesis of a completely tertiary mono-fatty alkyl polyalkylamine. Although the reaction path is mentioned, the reaction conditions are not clear and the product with only one fatty alkyl moiety appears to be pure. It is mentioned that the salt of completely tertiary mono-fatty alkyl triamine is suitable for use in the aqueous slow-setting asphalt aggregate mixture.

US 4,967,008 relates to mono-fatty alkyl polyalkylamines having primary, tertiary, and optionally secondary amine moieties. An exemplary product is linear N-tallow-N-methyldipropylene triamine. Because the intermediate in the method of US4967008 is methylated before the second cyanoethylation step, there is no branching in the product.

According to the CAS registration number 1623405-26-4, a linear di-fatty alkyl tetraamine is known, Its CAS name is "N'-{3-[(3-aminopropyl)amino]propyl}-N,N-di-C16-18 alkyl trimethylene diamine.

US2003/049310 discloses a large number of cationic lipids and their use in liposomes to introduce functional bioactive agents into culture cells. The mixture of polyamines as claimed is not disclosed or recommended.

Regarding lubricating oil, various amines have been evaluated in the past. Especially for 2-stroke marine engines, it is known that due to changes in emission regulations and due to the different fuels used, there is a need for a lubricating oil, especially for engines that burn sulfur-containing oil, especially for An improved amine formulation for lubricating oil for 2-stroke diesel marine engines.

It was unexpectedly discovered that a composition with a specific amount of linear and branched di-fatty alkane (en) tetraamines showed excellent properties when used in lubricating oils and other applications known to use polyalkylamines Such applications as deemulsifiers for oil-in-water emulsions, as corrosion inhibitors, fuel additives, anti-scaling agents, asphalt additives, enhanced oil recovery from oil wells, cutting oil additives and antistatic agents for general use. In addition, it has been found that the claimed method for the preparation of a difatty alk(en)tetraamine is very economical in the preparation of the desired composition.

Therefore, the present invention relates to such a di-fatty alk(en)-based polyalkylamine composition, which comprises a mixture of: one or more polyalkylamines selected from the products of formula (I) and (II)

1，且其中該混合物包含至少5重量%之具有純直鏈結構的產物。發現具有直鏈及分支鏈產物的此類混合物具有所期望的黏度概況。 Where each R is independent of the other R is a linear or branched aliphatic alkyl or aliphatic alkenyl moiety, defined herein as having 8-22 carbon atoms, n and z are independently 0, 1, 2 or 3, and when When z>0, then o and p are independently 0, 1, 2, or 3, or derivatives thereof, wherein the mixture contains at least 3% by weight of branched chain products, wherein at least one of n and z

1, and wherein the mixture contains at least 5% by weight of a product with a pure linear structure. It was found that such mixtures with linear and branched products have the desired viscosity profile.

In one embodiment, the amount of the product having a linear structure in the mixture is 6, 7.5, 10, or 14% by weight or more based on the weight of the total polyalkylamine. In one embodiment, the linear product in the mixture has formula (I), where n and z are zero. In one example, the linear product in the mixture has formula (II), where n is zero.

1。此對式(II)之產物而 言意謂著對於分支鏈產物n必須

1。 In one embodiment, based on the weight of the total polyalkylamine, the mixture contains at least 4% by weight (%w/w), suitably at least 5%w/w, suitably at least 6%w/w, suitably greater than 7%w/w, suitably greater than 7.5%w/w, suitably greater than 10%w/w, suitably greater than 20%w/w branched chain compound, for the product of formula (I), one of n and z At least one

1. For the product of formula (II), it means that for the branched chain product n must

1.

It should be noted that as long as n, o, p, or z is 0, hydrogen is covalently bonded to nitrogen. For economic reasons, each of n, o, p, and z is independently and when it is not 0, it is 1 or 2, preferably 1.

Although the two R groups may be different, in one embodiment they are the same because it is more economical to prepare such materials. Regardless of whether they are the same, one or both of the R groups independently are usually obtained from chemical raw materials or from natural sources, such as from natural oils and fats. In particular, if a natural source is used, it means that the carbon chain length of each R group may have a specific distribution. Suitably, R is derived from animal and vegetable oils and fats, such as tallow, cocoa and palm oil. Since the preparation of the di-fatty alk(en)-based polyalkylamines according to the present invention involves a hydrogenation step, it may be beneficial to use hydrogenated R groups before using the claimed method to prepare the products of the present invention. However, for some raw materials, even after hydrogenation, a significant amount of unsaturated bonds may remain. Suitably, a fully hydrogenated tallow group is used as the R group and forms the corresponding mixture of di-fatty alkyl polyalkylamines. Alternatively, the raw material for the R group is unsaturated, so that the unsaturated R group can be fully or partially hydrogenated during the process to prepare the claimed disaliphatic alk (en)-based polyalkylene amine, which is a disaliphatic A mixture of polyalkylene amines and di-fatty alkenyl polyalkylene amines. Products with one fully saturated R group and one unsaturated R group are also products of the present invention.

Therefore, as used herein, "di-fatty alkyl (en)-based polyalkylamine" refers to di-fatty alkyl polyalkyl amine, di-fatty alkenyl polyalkyl amine, fatty alkyl fatty alkenyl polyalkyl amine And its mixtures.

The term "composition" used anywhere in this article also covers "basic composition", but may be limited to its strict meaning of "complete composition" as appropriate.

Throughout the description of this specification and the scope of the patent application, the words "comprise" and "contain" and their variants (such as "comprising" and "including" (Comprises)") means "including (but not limited to)" and does not exclude other parts, additives, components, integers or steps. In addition, unless the context requires otherwise, the singular form encompasses the plural form; in particular, where the indefinite article is used, unless otherwise required herein, this specification should be understood to cover the plural as well as the singular.

In a case where an upper limit and a lower limit are proposed for a characteristic, for example, the concentration of a component, a series of values defined by a combination of any one of the upper limit and any one of the lower limit may also be implicit.

It should be understood that the various aspects and examples of the detailed description as disclosed herein illustrate specific ways for preparing and using the present invention and do not limit the scope of the present invention when considered in conjunction with the scope of patent application and the detailed description. It should also be understood that features from different aspects and embodiments of the present invention can be combined with features from different aspects and embodiments of the present invention.

The derivative of the di-fatty alkyl (en)-based polyalkylamine composition of the present invention includes one or more of the NH moieties of the dialkyl polyalkylamine of the present invention are methylated, alkoxylated or methylated. Alkylated and alkoxylated products. It has been found that such products have the desired solubility of dialkyl polyalkylamines, especially in lubricating oils. Alkoxylated derivatives are suitably butoxylated, propoxylated and/or ethoxylated. If two or more different alkoxylating agents are used, they can be used in any order, such as EO-PO-EO, and various alkoxy units can have block properties and/or exist in a random manner. Suitably, the primary -NH ₂ group is alkoxylated in a conventional manner with one or more alkylene oxides to form a -NH-AO-H group, where AO represents one or more alkylene-oxy units. The resulting -NH-AO-H group can be further alkoxylated to form a -N(AO-H) ₂ group. Especially when a large amount of alkylene oxide is used (that is, when there are more than 8 AO molecules per polyalkylamine molecule), usually one or more of the secondary amine functional groups (if present) are also alkoxylated of. In one embodiment, all primary and secondary amine functional groups of the dialkyl polyamine are alkoxylated. In another embodiment, the disaliphatic alk(en)-based polyalkylamine is derived by methylating one or more of the NH functional groups in a conventional manner, for example, by reacting with formic acid and formaldehyde. In another embodiment, one or more of the OH functional groups of the alkoxylated di-fatty alk(en)-based polyalkylamine are methylated in a conventional manner.

Although the present inventors do not wish to be bound by the following theories, it is believed that when compared with fully branched or fully linear products, the advantageous properties of the dialkyl polyalkylamine composition as claimed lie in the composition The special interaction of amines. More specifically, it is believed that a mixture of linear and branched chain products is a component used to achieve the desired combination of rheological and anti-corrosion properties of the fluid in which the composition is used.

In view of this theory, products with a variety of different branched molecules may be preferred. In this case, a composition comprising a mixture of polyalkylamines of formula (I) is preferred. However, because the preparation cost of a composition containing a mixture of polyalkylamines of formula (II) can be lower, under certain circumstances, a composition containing a mixture of polyalkylamines of formula (II) may be better of. If appropriate, a composition comprising a mixture of dialkyl(en)-based polyalkylamines of formula (I) and (II) is used.

In one embodiment, the present invention relates to the use of a composition comprising a branched chain product and a linear product (wherein n and z are 0) according to formula (I), and it is found that the composition also exhibits the desired rheological properties and characteristic.

The claimed composition is suitably used as a deemulsifier for oil-in-water emulsions, corrosion inhibitors, fuel additives, anti-scaling agents, asphalt additives, enhanced oil recovery agents from oil wells, cutting oil additives, antistatic agents and lubricating oils Additives in oil, especially in lubricating oils used in machines with varying amounts of acidic contaminants, especially sulfuric acid. One area of interest is the 2-stroke marine diesel engine, which depends on availability, price, and environmental regulations, which usually use different fuels each with a different sulfur content to operate.

The mixture of dialkyl(en)-based polyalkylamines as claimed can be produced using conventional method steps, which are carried out in the order and manner in which the claimed mixture is obtained. Appropriate preparation of the claimed compound The method is described in the following experimental part. The diamine is used as the starting material and involves two or more cycles. For economic reasons, two are preferred. Each has a cyanoethylation step and a hydrogenation step, which are hereinafter referred to as two cycles method. However, alternative methods where one equivalent of dialkyldiamine is reacted with two or more equivalents of acrylonitrile in one step, followed by hydrogenation and, if appropriate, other recycling methods involving cyanoethylation and hydrogenation steps are advantageous. , Because it requires fewer reaction steps.

In the two-cycle method, to improve branching, acidic catalysts such as HCl or acetic acid are used. In addition, increasing the reaction temperature during cyanoethylation in this method will result in increased branching. In the embodiment of the multiple cycle method, the temperature of the later cyanoethylation step is higher than the temperature of the earlier cyanoethylation step to obtain a product with the desired branching. In one example, more than 1 mole of acrylonitrile was used per mole of starting polyamine, and it was also found that it increased the branching of the resulting product to a desired degree.

The temperature in each cyanoethylation step is appropriately selected in the range of 70 to 125°C. In one embodiment, for economic reasons, the reaction is carried out at temperatures up to 80, 85, 90, 95, or 100°C.

In order to maintain a homogeneous reaction mixture, a solvent is appropriately used. Suitable solvents include C _1-4 alcohols and C _2-4 diols. Ethanol can be used as a solvent for ease of operation. Unexpectedly, it was discovered that C _1-4 alcohols and C _2-4 diols are not only solvents. It was found that it also has co-catalytic activity in the cyanoethylation step.

The amount of solvent to be used can vary within a wide range. For economic purposes, this amount is usually kept to a minimum. The amount of solvent, especially in the cyanoethylation step, is suitably less than 50, 40, 30 or 25% by weight of the liquid reaction mixture. The amount of solvent, especially in the cyanoethylation step, is suitably greater than 0.1, 0.5, 1, 5 or 10% by weight of the liquid reaction mixture.

It has been found that the di-aliphatic alk(en)-based polyalkylamine composition of the present invention is particularly suitable as a corrosion inhibitor, especially in cutting oils and lubricating oils. However, it is also suitably used as an oil-in-water emulsion Deemulsifiers, fuel additives, anti-scaling agents, asphalt additives, enhanced oil recovery agents used in oil wells and as antistatic agents.

experiment

Duomeen® 2HT was purchased from AkzoNobel.

Unless otherwise noted, other chemicals are derived from Sigma Aldrich.

Example 1

A 1L glass reactor with a turbo stirrer was used to prepare a fully branched product with 4 amine functional groups, in which a Prominent Gamma/L membrane pump was used to administer chemicals and a Lauda K6KP heating bath was used to control the constant temperature.

Raw materials

Steps and results

其中HT代表氫化動物脂。 The cyano group is performed by feeding Duomeen 2HT, isopropanol (co-catalyst and solvent for the formed dicyano product), water and HCl into the reactor, and then giving acrylonitrile within about three hours. -Ethylation step. Reaction path:

Wherein HT stands for hydrogenated tallow.

After 80% conversion, the reaction rate was so slow that the reaction stopped. A vacuum was applied to the reactor and the temperature was increased to 110°C to remove acrylonitrile, water and IPA. The product was washed and neutralized with a 4% Na ₂ CO ₃ solution in two steps to remove all HCl, and then hydrogenated using the same equipment. Reaction path:

A conventional Raney cobalt catalyst, such as A-7000 from Johnson Matthey or Acticat® 1100 from CatAlloy, is fed into the stirred reactor containing the dicyano product, and then heated to 130 while bubbling with nitrogen °C to remove traces of acrylonitrile and water. The reactor was then fed with ammonia (13-14 barg) while maintaining the temperature at 105°C. The reactor was then heated to 150°C and hydrogen was added to maintain a pressure of 49 barg. After the reaction was completed, the temperature was lowered to 80°C and nitrogen was used to flush out residual hydrogen and ammonia.

The resulting composition was analyzed by GC-MS and found to contain >70% of the product of formula (II) 2HTY (where n=1), and more than 14% w/w of the linear product (HT) ₂ N-(CH ₂ ) ₃ -NH-(CH ₂ ) ₃ -NH ₂ , a small amount of starting product (HT) ₂ N-(CH ₂ ) ₃ -NH ₂ and some other unidentified alkylamines.

Examples 2a and 2b

A mixture of linear and branched products (Tetrameen 2HTb) was prepared by a two-cycle procedure, where the above cyano-ethylation and hydrogenation steps were repeated. Combine 0.6 mol of Duomeen 2HT with 0.65 mol of acrylonitrile and react in the first cyano-ethylation step. After hydrogenation, the triamine was combined and reacted with another 0.65 moles of acrylonitrile. At the end of each cyano-ethylation step, NMR was used to analyze the reaction mixture and determine whether one mole of acrylonitrile was reacted per mole of starting material. If the reaction is found to be too low, give some additional acrylonitrile and repeat the analysis after 1 hour. Repeat this cycle until the desired response is obtained. Use GC-MS to apply the following conditions to analyze the final product

In the example, for Examples 2a and 2b, no additional acrylonitrile was added after the first cyanoethylation step performed at temperatures of 85°C and 75°C, respectively. For Examples 2a and 2b, in the second cyanoethylation step, the temperature was 85 and 80°C, respectively. In Example 2a, an additional 0.025 mol of acrylonitrile was required to complete the second cyanoethylation step, while in Example 2b, an additional 0.12 mol of acrylonitrile was added before the addition of 0.60 mol of acrylonitrile was achieved. Acrylonitrile. The highest amount of branching was observed in the sample 2a with the highest temperature.

1，且亦含有超過14%w/w之直鏈產物，其中n=z=0。 It has been confirmed that the off-white product that is a paste/viscous liquid at room temperature contains more than 13.8% w/w of the branched chain product of formula (I), wherein one or more of n and z

1. It also contains more than 14% w/w linear products, where n=z=0.

Example 3-5

To a commercial lubricant (Talusia HR70, which is hyperbasic and contains CaCO ₃ , from Total Lube Marine), 5wt% of 2HTb, 2HTY or a 50/50 blend of 2HTY and 2HTb of Example 2a was added and mixed thoroughly, and then The 50BN point of the lubricant composition was neutralized with 95% sulfuric acid in order to simulate the neutralization phenomenon of the composition to be closer to the real conditions of using the lubricating composition in marine engines.

In this method, amines along with super-alkalizing detergents neutralize sulfuric acid. The generated sulfate ion becomes a counter ion of positively charged ammonium group and/or _{reacts with calcium ion of CaCO 3} to form gypsum, CaSO ₄ .

The viscosity (Pa.s) of the three acidified blends of lubricant and alkyl polyamine prepared as above at 40°C was measured by measuring the viscosity at 0.05 s-1 as shown in the table Viscosity at shear rate. All measurements are performed on the AR-G2 rheometer from TA-instruments at 40°C.

All these samples showed acceptable viscosity.

Comparative example A-C

Analyze the performance of AkzoNobel's commercial monooleyl tripropylene tetramine (Tetrameen OV) and AkzoNobel's commercial monotallow tripropylene tetramine (Tetrameen T) in lubricants prepared as described for Examples 3-5 Acidify the viscosity of the blend and compare it with the viscosity of the 2HTb blend and the lubricant alone.

Table 2

The results showed that Tetrameen OV and Tetrameen T resulted in unacceptable viscosity of the acidified blend.

Comparative example D-F

The commercial dihydrogenated tallow dipropylene triamine (Triameen® 2HT) of AkzoNobel and the commercial dihydrogenated tallow propylene diamine (Duomeen® 2HT) of AkzoNobel prepared as described for Examples 3-5 in the lubricant Acidified the blend, where the amount of triamine was increased to 6.2% w/w and the amount of Duomeen was increased to 8% w/w to achieve the same total base number, the viscosity of the blend was analyzed and compared with the comparative example AC Comparison of the viscosity of the blends. It was found that the viscosity (Pa.s) at a shear rate of 0.05 s-1 was between the viscosity of Tetrameen OV and Tetrameen T, thus showing an improperly high viscosity again.

Example 6

In this example, the compounds of Examples 1, 2a and 2b are used as deemulsifiers, corrosion inhibitors, fuel additives, antifouling agents, asphalt additives, enhanced oil recovery agents for oil wells, and cutting agents for oil-in-water emulsions. Oil additives and antistatic agents. It shows typical performance, but also shows an unexpected viscosity profile for a disaliphatic alk(en)-based polyalkylamine with this molecular weight.

Claims (18)

A di-fatty alk(en)-based polyalkylamine composition comprising a mixture of the following: polyalkylamines selected from products of formula (I) and (II)

Where each R is independent of the other R is an alkyl or alkenyl moiety with 8-22 carbon atoms, n and z are independently 0, 1, 2 or 3, and when z>0, then o and p are each other Independently 0, 1, 2, or 3, or derivatives thereof, wherein the mixture comprises a) a total of at least 3% by weight of the branched chain compound of formula (I), wherein at least one of n and z

1, and the product of formula (II), where n

1, and b) A total of at least 5% by weight of the product of formula (I), where n and z=0, and the compound of formula (II), where n=0. Such as the polyalkylamine composition of claim 1, which contains a total of at least 4% w/w of the branched chain compound of formula (I), wherein at least one of n and z is not 0, and the formula (II) Compound, where n is not 0. Such as the polyalkylamine composition of claim 1 or 2, which contains at least 5% by weight of products of formula (I) and (II) having a linear structure, wherein n in formula (I) and (II) Is 0 and z in formula (I) is 0. Such as the polyalkylamine composition of claim 1 or 2, which comprises a derivative of a di-fatty alkyl(en)-based polyalkylamine, wherein the derivatives are optionally methylated alkoxylates. The polyalkylamine composition of claim 4, which comprises at least 5% by weight of products of formula (I) and (II) having a linear structure, wherein n in formula (I) and (II) is 0 And z in formula (I) is 0. The polyalkylamine composition of claim 1 or 2, which comprises a derivative of a di-fatty alkyl(en)-based polyalkylamine, wherein the derivatives are methylated. The polyalkylamine composition of claim 6, which contains at least 5 wt% of products of formula (I) and (II) having a linear structure, wherein n in formula (I) and (II) is 0 And z in formula (I) is 0. A method for preparing a polyalkylamine composition as claimed in any one of claims 1 to 7, wherein the dialliphatic alk(en)alkyldiamine is reacted in two or more cycles, wherein each cycle It includes a cyanoethylation step and a subsequent hydrogenation step. The method of claim 8, wherein an acid catalyst is used during the cyanoethylation steps. The method of claim 8 or 9, wherein the reaction temperature during the later cyanoethylation step is higher than the temperature during the earlier cyanoethylation step. Such as the method of claim 8 or 9, wherein more than 1 mole of acrylonitrile is used per mole of starting polyamine. The method of claim 11, wherein the reaction temperature during the later cyanoethylation step is higher than the temperature during the earlier cyanoethylation step. A method for preparing a polyalkylamine composition as claimed in any one of claims 1 to 7, wherein the dialliphatic alk(en)alkyldiamine undergoes a cyanoethylation step and a subsequent hydrogenation step, wherein In the cyanoethylation step, at least 2 moles of acrylonitrile is used per mole of the dialiphatic alk(en)alkyl diamine and an acid catalyst is used. The method of claim 13, wherein the product further undergoes one or more cycles including cyanoethylation and subsequent hydrogenation steps. The method according to any one of claims 8, 9, 13 and 14, wherein one or more solvents _{selected from C 1-4} alcohols and C _{2-4 diols are present in the cyanoethylation step.} The method of claim 15, wherein the amount of the solvent is 0.1 to 50% by weight of the liquid reaction mixture. A method for preparing a derivative as described in claim 4 or 6, which is a method as in any one of claims 8 to 16 with an additional step, wherein in the additional step, the difatty alkane (ene )-Based polyalkylamines are methylated, alkoxylated or both. A use of a di-fatty alkane (en)-based polyalkylamine composition as claimed in any one of claims 1 to 7, which is used as a deemulsifier, corrosion inhibitor, fuel additive, anti-corrosion agent for oil-in-water emulsions Scaling agents, asphalt additives, enhanced oil recovery agents used in oil wells, cutting oil additives or antistatic agents.